JPS624699B2 - - Google Patents
Info
- Publication number
- JPS624699B2 JPS624699B2 JP54046949A JP4694979A JPS624699B2 JP S624699 B2 JPS624699 B2 JP S624699B2 JP 54046949 A JP54046949 A JP 54046949A JP 4694979 A JP4694979 A JP 4694979A JP S624699 B2 JPS624699 B2 JP S624699B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- image
- compounds
- heterocyclic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 silver halide Chemical class 0.000 claims description 65
- 150000001875 compounds Chemical group 0.000 claims description 59
- 239000000839 emulsion Substances 0.000 claims description 58
- 229910052709 silver Inorganic materials 0.000 claims description 50
- 239000004332 silver Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000000623 heterocyclic group Chemical group 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 15
- 150000001450 anions Chemical group 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 125000004442 acylamino group Chemical group 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 5
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 4
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000005521 carbonamide group Chemical group 0.000 claims description 3
- 125000000565 sulfonamide group Chemical group 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 47
- 239000000243 solution Substances 0.000 description 24
- 239000000975 dye Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 22
- 239000002667 nucleating agent Substances 0.000 description 21
- 238000011161 development Methods 0.000 description 18
- 108010010803 Gelatin Proteins 0.000 description 17
- 229920000159 gelatin Polymers 0.000 description 17
- 239000008273 gelatin Substances 0.000 description 17
- 235000019322 gelatine Nutrition 0.000 description 17
- 235000011852 gelatine desserts Nutrition 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 238000012545 processing Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 150000003839 salts Chemical group 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LFOIDLOIBZFWDO-UHFFFAOYSA-N 2-methoxy-6-[6-methoxy-4-[(3-phenylmethoxyphenyl)methoxy]-1-benzofuran-2-yl]imidazo[2,1-b][1,3,4]thiadiazole Chemical compound N1=C2SC(OC)=NN2C=C1C(OC1=CC(OC)=C2)=CC1=C2OCC(C=1)=CC=CC=1OCC1=CC=CC=C1 LFOIDLOIBZFWDO-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- XWYLXEIXVJBLRS-UHFFFAOYSA-N 1-phenacylpyridin-1-ium-3-carboxamide;bromide Chemical compound [Br-].NC(=O)C1=CC=C[N+](CC(=O)C=2C=CC=CC=2)=C1 XWYLXEIXVJBLRS-UHFFFAOYSA-N 0.000 description 2
- CRTGSPPMTACQBL-UHFFFAOYSA-N 2,3-dihydroxycyclopent-2-en-1-one Chemical compound OC1=C(O)C(=O)CC1 CRTGSPPMTACQBL-UHFFFAOYSA-N 0.000 description 2
- IFTCIJGLDWOLSB-UHFFFAOYSA-N 2-pentadecylbenzene-1,4-diol Chemical compound CCCCCCCCCCCCCCCC1=CC(O)=CC=C1O IFTCIJGLDWOLSB-UHFFFAOYSA-N 0.000 description 2
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- INVVMIXYILXINW-UHFFFAOYSA-N 5-methyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Chemical compound CC1=CC(=O)N2NC=NC2=N1 INVVMIXYILXINW-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000012992 electron transfer agent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UQVGEBKEKXJAKD-UHFFFAOYSA-N n-hexadecylpyridine-3-carboxamide Chemical compound CCCCCCCCCCCCCCCCNC(=O)C1=CC=CN=C1 UQVGEBKEKXJAKD-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- SFXOHDOEOSCUCT-UHFFFAOYSA-N styrene;hydrochloride Chemical compound Cl.C=CC1=CC=CC=C1 SFXOHDOEOSCUCT-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- QLDQYRDCPNBPII-UHFFFAOYSA-N 1,2-benzoxazol-3-one Chemical class C1=CC=C2C(O)=NOC2=C1 QLDQYRDCPNBPII-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- SOBDFTUDYRPGJY-UHFFFAOYSA-N 1,3-bis(ethenylsulfonyl)propan-2-ol Chemical compound C=CS(=O)(=O)CC(O)CS(=O)(=O)C=C SOBDFTUDYRPGJY-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- PXSUMUYPXZEXDT-UHFFFAOYSA-M 1-phenyl-2-pyridin-1-ium-1-ylethanone;bromide Chemical compound [Br-].C=1C=CC=CC=1C(=O)C[N+]1=CC=CC=C1 PXSUMUYPXZEXDT-UHFFFAOYSA-M 0.000 description 1
- OPOJRMTZHYUKLY-UHFFFAOYSA-N 1h-1,3,5-triazin-2-one Chemical compound O=C1N=CN=CN1 OPOJRMTZHYUKLY-UHFFFAOYSA-N 0.000 description 1
- XPACYYBVTUJCQR-UHFFFAOYSA-N 2,3,5,6-tetramethoxybenzene-1,4-diol Chemical compound COC1=C(O)C(OC)=C(OC)C(O)=C1OC XPACYYBVTUJCQR-UHFFFAOYSA-N 0.000 description 1
- SVTFGFLBXLUFME-UHFFFAOYSA-N 2,5-dihydroxy-4-octadecan-2-ylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCC(C)C1=CC(O)=C(S(O)(=O)=O)C=C1O SVTFGFLBXLUFME-UHFFFAOYSA-N 0.000 description 1
- ZKEGGSPWBGCPNF-UHFFFAOYSA-N 2,5-dihydroxy-5-methyl-3-(piperidin-1-ylamino)cyclopent-2-en-1-one Chemical compound O=C1C(C)(O)CC(NN2CCCCC2)=C1O ZKEGGSPWBGCPNF-UHFFFAOYSA-N 0.000 description 1
- RDMIJQCFPQDYQN-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)benzene-1,4-diol Chemical compound CC(C)(C)CC(C)(C)C1=CC(O)=CC=C1O RDMIJQCFPQDYQN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical group NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- ZZXILYOBAFPJNS-UHFFFAOYSA-N 2-octylbenzene-1,4-diol Chemical compound CCCCCCCCC1=CC(O)=CC=C1O ZZXILYOBAFPJNS-UHFFFAOYSA-N 0.000 description 1
- AJKLCDRWGVLVSH-UHFFFAOYSA-N 4,4-bis(hydroxymethyl)-1-phenylpyrazolidin-3-one Chemical class N1C(=O)C(CO)(CO)CN1C1=CC=CC=C1 AJKLCDRWGVLVSH-UHFFFAOYSA-N 0.000 description 1
- SJSJAWHHGDPBOC-UHFFFAOYSA-N 4,4-dimethyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(C)CN1C1=CC=CC=C1 SJSJAWHHGDPBOC-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZLICXUZNFMMVHQ-UHFFFAOYSA-M CC1=NC(C=CC=C2)=C2[S+]1CCC=O.[Br-] Chemical compound CC1=NC(C=CC=C2)=C2[S+]1CCC=O.[Br-] ZLICXUZNFMMVHQ-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229940072107 ascorbate Drugs 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- OIPQUBBCOVJSNS-UHFFFAOYSA-L bromo(iodo)silver Chemical compound Br[Ag]I OIPQUBBCOVJSNS-UHFFFAOYSA-L 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- XXTZHYXQVWRADW-UHFFFAOYSA-N diazomethanone Chemical compound [N]N=C=O XXTZHYXQVWRADW-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- SUNVJLYYDZCIIK-UHFFFAOYSA-N durohydroquinone Chemical compound CC1=C(C)C(O)=C(C)C(C)=C1O SUNVJLYYDZCIIK-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- MSYBLBLAMDYKKZ-UHFFFAOYSA-N hydron;pyridine-3-carbonyl chloride;chloride Chemical compound Cl.ClC(=O)C1=CC=CN=C1 MSYBLBLAMDYKKZ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PTFYQSWHBLOXRZ-UHFFFAOYSA-N imidazo[4,5-e]indazole Chemical class C1=CC2=NC=NC2=C2C=NN=C21 PTFYQSWHBLOXRZ-UHFFFAOYSA-N 0.000 description 1
- LOCAIGRSOJUCTB-UHFFFAOYSA-N indazol-3-one Chemical class C1=CC=C2C(=O)N=NC2=C1 LOCAIGRSOJUCTB-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- SKDQTLDBZMLKQA-UHFFFAOYSA-N n-[4-(phenylcarbamothioylamino)anilino]formamide Chemical compound C1=CC(NNC=O)=CC=C1NC(=S)NC1=CC=CC=C1 SKDQTLDBZMLKQA-UHFFFAOYSA-N 0.000 description 1
- BWJFEONZAZSPSG-UHFFFAOYSA-N n-amino-n-(4-methylphenyl)formamide Chemical compound CC1=CC=C(N(N)C=O)C=C1 BWJFEONZAZSPSG-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007248 oxidative elimination reaction Methods 0.000 description 1
- 150000004989 p-phenylenediamines Chemical group 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- ZXAVCWNHDVCJTA-UHFFFAOYSA-M potassium;2,5-dihydroxy-4-pentadecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCCCCC1=CC(O)=C(S([O-])(=O)=O)C=C1O ZXAVCWNHDVCJTA-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical class N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/485—Direct positive emulsions
- G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure
- G03C1/48546—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure characterised by the nucleating/fogging agent
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/50—Reversal development; Contact processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
本発明は、ハロゲン化銀写真乳剤の現像方法に
係り、さらに詳細には内部潜像型ハロゲン化銀乳
剤を用いて直接にポジ像を形成させる現像方法に
関するものである。
画像的露光の後の一回の現像によつて直接にポ
ジ（反転）像を得るいくつかの写真過程はよく知
られている。その１つとして内部潜像型ハロゲン
化銀乳剤を用いる方法が知られている。この方法
では、ハロゲン化銀粒子の内部に選択的に潜像を
形成するハロゲン化銀写真乳剤（内部潜像型ハロ
ゲン化銀乳剤）を画像的露光の後に、均一露光に
よりまたはヒドラジンのような核形成剤の作用に
より粒子表面に現像核を形成し、表面現像液によ
つて処理することによつてポジ（反転）像を得
る。この方法は内部像反転法と呼ばれ、例えば
The Theory of Photographic Process（第４
版、1977年、T.H.James編）第187頁に原理が記
載されている。
内部像反転法に使用される核形成剤（またはカ
ブラシ剤）は、現像液中に含有させるかまたは感
光材料中、特にハロゲン化銀乳剤層中、に内蔵さ
せる。核形成剤としては東独特許5024号、米国特
許2563785号、同2588982号、同2604440号、同
3227552号、同4030925号、同4080207号、リサー
チ デスクロージヤ（Research Disclosure）
15164、P.76〜77（構造式及び）に記載させ
ているようなヒドラジン類及びその誘導体、なら
びに米国特許3615615号、同3718470号、同
3719494号、同3734738号、同3330655号、同
4094683号に記載されているようなヘテロ環４級
アンモニウム化合物、等が知られている。しかし
従来のこれらの核形成剤は、特にハロゲン化銀乳
剤層に組込まれたときには、良好な写真性能（特
に高いDmax／Dmin比）を与えない、ハロゲン
化銀乳剤の保存安定性を害う、特に高露光量域で
ネガ像を誘発し易い、処理時に気体を発生させ画
像を均一性を害う、化合物が不安定で条件によつ
てはその作用を失う、他の乳剤添加剤と反応しや
すくその作用を失う、ハイライト部分にステイン
を生じる、現像時に長い誘導期を与えるとか充分
な現像速度を与えない、純粋な形で合成し難いと
かの欠点のいづれかをもつていて、決して満足で
きるものではなかつた。
本発明の目的は第１に、画像的に露光された内
部潜像型ハロゲン化銀乳剤から良好な写真性能、
特に高いDmax.と低いDmin.と、を形成する反転
現像方法を提供することである。
本発明の目的は第２に、感光材料中に核形成剤
を安定な形で含有せしめ、単に現像薬のアルカリ
性水溶液によつて処理することによつて一定した
結果を得ることができる反転像形成方法を提供す
ることである。
本発明の目的は第３に、核形成剤を含有する現
像薬のアルカリ性水溶液によつて感光材料を処理
する反転像形成方法を提供することである。
本発明の目的は第４に、カプラーを含有するハ
ロゲン化銀乳剤層をもつ感光材料中を核形成剤の
存在のもとで現像薬のアルカリ性水溶液によつて
処理することによつてカラー反転像を形成する方
法を提供することである。
本発明の目的は第５に、拡散性色素によつて転
写画像を形成する色素像形成材料と組合つた内部
潜像型ハロゲン化銀乳剤層をもつ感光材料を核形
成剤の存在のもとで、現像薬のアルカリ性水溶液
によつて処理することによつて転写されたカラー
反転像を形成する方法を提供することである。
本発明のこの他の目的は、本発明の詳細な説明
から理解されよう。
これらの発明の目的は、ハロゲン化銀粒子の内
部に選択的に潜像を形成するハロゲン化銀写真乳
剤の少くとも１つを支持体上にもつ感光材料を、
画像露光の後に、下記一般式〔〕又は〔〕で
表わされる化合物から選ばれる少くとも１の化合
物を含有するアルカリ性現像液によつて現像する
方法、又は、該化合物と組合わされた、ハロゲン
化銀粒子の内部に選択的に潜像を形成するハロゲ
ン化銀写真乳剤の層の少なくとも１つを支持体上
にもつ感光材料を画像露光の後にアルカリ性現像
液によつて現像する方法によつて達成された。
式中、ｎは０、１、２もしくは３の整数を表わ
し、R1は３位、４位もしくは５位に位置する置
換基であつて、ハロゲン原子、トリハロメチル
基、シアノ基、カルバモイル基、カルボン酸エス
テル基、カルボンアミド基、スルフオンアミド
基、アシル基、スルホニル基、スルフアモイル
基、アシルアミノ基、アリール基、アルキル基、
アルケニル基、ヘテロ環基よりなる群から選ばれ
る基を表わす。
但し、R1が４位の置換基である場合は、R1は
α−水素をもつアルキル基もしくはハロゲン原子
であることはない。
R2はアリール基、ヘテロ環基もしくはアルキ
ル基を表わす。Ｘはアニオンを表わす。
R1もしくはR2は、上記の置換基の２個以上が
連結基によつて結合された多価の残基もしくはポ
リマー残基を表し得る。またR1もしくはR2は炭
素数８以上の疎水性のバラスト基をもつ残基を表
わしてもよい。また隣接する２つのR1は環、特
に５員または６員の環を形成してもよい。ここで
バラスト基は炭素数８から約30までの、アルキル
基またはアルキルアリール基をもつ疎水性残基例
えばオクチル基、ドデシル基などを表わす。
一般式〔〕および〔〕で表わされる化合物
のピリジニウム窒素とシアノもしくはアシル基と
にはさまれるメチレン基の水素原子は、W.G.
Phillipsらの報告（J.Org.Chem.35巻、3144頁）
によつて例示されているようにプロトンとして電
離し得て、反応活性のＮ−イリドを与える。一般
式〔〕および〔〕の化合物がどのようにして
内部潜像型乳剤の反転現像をひき起すか、ないし
は促進するかという機構は明確にされていない
が、有効な化合物のpKa値は使用現像液のPH値の
近くまたはそれ以下に位置することから、解離形
またはそれから誘導される活性体が作用すると考
察される。解離形は
The present invention relates to a method for developing a silver halide photographic emulsion, and more particularly to a method for directly forming a positive image using an internal latent image type silver halide emulsion. Several photographic processes are well known in which a positive (reverse) image is obtained directly by a single development after imagewise exposure. One known method is to use an internal latent image type silver halide emulsion. In this method, a silver halide photographic emulsion (internal latent image type silver halide emulsion) that selectively forms a latent image inside the silver halide grains is applied after imagewise exposure, and then uniformly exposed or Development nuclei are formed on the particle surface by the action of the forming agent, and a positive (reversal) image is obtained by processing the surface with a developer. This method is called internal image inversion method, for example
The Theory of Photographic Process (Part 4)
The principle is described on page 187 (Ed., 1977, edited by TH James). The nucleating agent (or fogging agent) used in the internal image reversal method is contained in the developer or incorporated into the light-sensitive material, particularly in the silver halide emulsion layer. As a nucleating agent, East German Patent No. 5024, U.S. Patent No. 2563785, U.S. Patent No. 2588982, U.S. Patent No. 2604440,
No. 3227552, No. 4030925, No. 4080207, Research Disclosure
15164, P.76-77 (structural formulas and) and derivatives thereof, as well as U.S. Pat.
No. 3719494, No. 3734738, No. 3330655, No. 3719494, No. 3734738, No. 3330655, No.
Heterocyclic quaternary ammonium compounds such as those described in No. 4094683 are known. However, these conventional nucleating agents, especially when incorporated into the silver halide emulsion layer, do not give good photographic performance (especially high Dmax/Dmin ratio), impair the storage stability of the silver halide emulsion, It tends to cause negative images, especially in high exposure ranges, it generates gas during processing and impairs image uniformity, the compound is unstable and loses its effect under certain conditions, and it reacts with other emulsion additives. They have the following disadvantages: they easily lose their effect, they cause stains in highlighted areas, they do not provide a long induction period or sufficient development speed during development, and they are difficult to synthesize in a pure form, so they are never satisfactory. It wasn't something. The first object of the present invention is to obtain good photographic performance from imagewise exposed internal latent image type silver halide emulsions.
It is an object of the present invention to provide a reversal development method that produces particularly high Dmax. and low Dmin. A second object of the present invention is to form a reversal image by stably containing a nucleating agent in a light-sensitive material and by simply processing with an alkaline aqueous developer solution. The purpose is to provide a method. A third object of the present invention is to provide a reversal image forming method in which a light-sensitive material is processed with an alkaline aqueous solution of a developer containing a nucleating agent. A fourth object of the present invention is to produce a color reversal image by treating a light-sensitive material having a silver halide emulsion layer containing a coupler with an alkaline aqueous solution of a developer in the presence of a nucleating agent. The objective is to provide a method for forming A fifth object of the present invention is to provide a light-sensitive material having an internal latent image type silver halide emulsion layer combined with a dye image-forming material that forms a transferred image using a diffusible dye in the presence of a nucleating agent. , a method of forming a transferred color reversal image by treatment with an alkaline aqueous solution of a developer. Other objects of the invention will be understood from the detailed description of the invention. The purpose of these inventions is to provide a photographic material having on a support at least one silver halide photographic emulsion that selectively forms a latent image inside silver halide grains.
A method of developing with an alkaline developer containing at least one compound selected from the compounds represented by the following general formula [] or [] after image exposure, or a silver halide in combination with the compound. This is achieved by a method in which a photosensitive material having on a support at least one layer of a silver halide photographic emulsion that selectively forms a latent image inside the grains is developed with an alkaline developer after imagewise exposure. Ta. In the formula, n represents an integer of 0, 1, 2 or 3, and R 1 is a substituent located at the 3rd, 4th or 5th position, and is a halogen atom, trihalomethyl group, cyano group, carbamoyl group, Carboxylic acid ester group, carbonamide group, sulfonamide group, acyl group, sulfonyl group, sulfamoyl group, acylamino group, aryl group, alkyl group,
Represents a group selected from the group consisting of alkenyl groups and heterocyclic groups. However, when R 1 is a substituent at the 4-position, R 1 is not an alkyl group having α-hydrogen or a halogen atom. R 2 represents an aryl group, a heterocyclic group or an alkyl group. X represents an anion. R 1 or R 2 may represent a polyvalent residue or a polymer residue in which two or more of the above substituents are linked via a linking group. Further, R 1 or R 2 may represent a residue having a hydrophobic ballast group having 8 or more carbon atoms. Further, two adjacent R 1 may form a ring, particularly a 5- or 6-membered ring. The ballast group here represents a hydrophobic residue having an alkyl or alkylaryl group having from 8 to about 30 carbon atoms, such as an octyl group or a dodecyl group. The hydrogen atom of the methylene group sandwiched between the pyridinium nitrogen and the cyano or acyl group of the compounds represented by the general formulas [] and [] is
Report by Phillips et al. (J.Org.Chem. vol. 35, p. 3144)
can be ionized as a proton to give a reactive N-ylide as exemplified by. The mechanism of how compounds of general formulas [] and [] cause or promote reversal development of internal latent image emulsions is not clear, but the pKa values of effective compounds are It is considered that the dissociated form or the active form derived therefrom acts because it is located near or below the pH value of the liquid. The dissociated form is
【式】 または【formula】 or
【式】の他にIn addition to [formula]
【式】または[expression] or
【式】のような互変異性体
も含むものとして理解すべきである。
本発明に使用される化合物は、弱酸性ないし中
性条件の感光材料中では主として活性の著しく低
い非解離形で組込まれ、現像のアルカリ性条件で
活性の高い解離形に変化し、感光材料の安定性の
維持と高い反転現像条件での活性の実現とを併せ
て実現できるように選択されることが有利であ
る。感光材料の型と現像条件等の要因に左右され
るが、一般に6.0以上好ましくは7.0以上で、好ま
しくは約11以下のpKa値に相当する酸性をもつ活
性メチレン基をもつ化合物が有用である。このよ
うな酸性度の調節は一般式〔〕と〔〕の置換
基R1とR2の適切な選択によつて達成できる。
本発明に使用される化合物は、前掲の公知のヘ
テロ環４級アンモニウム塩といくつかの点で明確
に区別される。即ち公知の化合物はヘテロ環アン
モニウム窒素原子に結合しているのが−CH2−
CH2−で代表される炭素数２以上のアルキレン基
が２つの活性化基との間に介在していて、このよ
うなアルキレン基の存在が核形成剤としての作用
にとつて必須要因を構成しているのに反し、本発
明の化合物は活性化基のアシル基との間にメチレ
ン基をもつという構造上の差異、並びに公知の４
級アンモニウム塩は作用に本質的な構造部分で中
性／アルカリ性の間で実質的に不変であるが、本
発明の化合物はその作用と密接に関係した仕方で
解離するという挙動上の差異は、本発明の化合物
を他の公知化合物群から明瞭に区別している。
さらに本発明に使用される化合物に類似の構造
の化合物の写真層への添加が、西独特許出願
（OLS）2448432号に開示されているが、本発明
の化合物はこの公開公報の化合物とも明瞭に区別
される。即ち同西独特許出願の化合物、特に化合
物８として記載されている２−Bromo−１−
phenacyl pyridinium bromide、はピリジニウム
環の２位にハロゲン原子をもちゼラチンと反応
し、内部潜像型ハロゲン化銀乳剤に対して現像の
とき核形成作用を示さない。
本発明の方法によれば高い最高濃度（Dmax）
と低い最小濃度（Dmin）とを兼ね備えた反転像
を得ることができる。このことは感光材料に含有
されるハロゲン化銀が高い比率で銀像に変換され
ることを意味し、この結果感光材料のハロゲン化
銀含有量の低減による経済的効果と省資源的効
果、並びに乳剤層の厚さの減少による画像の鮮鋭
度の改良と現像処理時間の短縮という写真性能の
向上効果が実現される。本発明の方法によれば、
省量の核形成剤で所定の写真効果が得られる、こ
のために核形成剤の使用に伴うステインの発生の
如き副次的マイナス効果を低く抑えることができ
る。本発明の方法によれば反転現像を短時間のう
ちに実現することができる。適切な置換基の選択
によれば充分な反転濃度を与えるに必要な量の核
形成剤を含有する乳剤層を安定に保つことができ
る。本発明の方法によれば、反転画像形成のとき
に、ヒドラジン系化合物に見られる窒素ガスの発
生のような気体発生による画像のムラの形成の必
配が全くない。また置換基の適切な選択によれ
ば、本発明は純粋な形で容易に合成でき、多くの
４級塩で見られる吸湿性とか保存上の不安定性と
かの心配の少い扱い易い化合物を使用することが
できる。本発明のこの他の特徴は、詳細な説明と
実施例とから明らかであろう。
本発明に使用される内部潜像型ハロゲン化銀乳
剤は、主にハロゲン化銀乳剤粒子内部に感光中心
をもつていて露光によつて選択的にそこに潜像を
形成し、これに対し粒子表面には潜像形成の程度
が低いものである。このような内部潜像型ハロゲ
ン化銀乳剤は、前掲のJamesの著書171〜176頁の
記述に従つて露光後に表面現像液によつて現像し
て得られる像の銀量（表面潜像に対応する）が、
内部現像液によつて得られる像の銀量（全潜像に
対応する）に比して明瞭に低い値を示すことによ
つて特徴づけられる。内部潜像型ハロゲン化銀乳
剤は種々の方法によつて作ることができる。例え
ば高ヨード含量をもち、アンモニヤ法で作られる
Burtonの乳剤（E.J.Wall著、ホトグラフイツク・
エマルジヨンズ（Photographic Emulsions）35
〜36頁、52〜53頁American Photographic
Publishing Co.、（1929年））および米国特許
2497875号、2563785号）、低ヨード含量をもちア
ンモニヤ法で作られる大粒子のプリミテイブ乳剤
（西独特許出願（OLS）2728108号）、ハロゲン化
銀−アンモニヤ錯塩溶液のアンモニヤ濃度の低下
を急激にしてハロゲン化銀粒子を沈澱させて作ら
れた乳剤（米国特許3511662）、最初に溶解性の高
い塩化銀のような銀塩粒子を作り、次いで溶解性
の低い（沃）臭化銀のような銀塩に変換するキヤ
スタストロフイー沈澱法によるコンバージヨン乳
剤（米国特許2592250号）、化学増感した大粒子の
コア乳剤に微粒子の乳剤を混合の上熟成すること
によつてコア粒子の上にハロゲン化銀のシエルを
被覆したコア・シエル乳剤（米国特許3206313
号、英国特許1011062号）、化学増感した単分散の
コア乳剤に銀イオン濃度を一定に保ちつつ可溶性
銀塩溶液と可溶性ハロゲン化物溶液とを同時に添
加してコア粒子の上にハロゲン化銀のシエルを被
覆したコア・シエル乳剤（英国特許1027146、米
国特許3761276）、乳剤粒子が２つ以上の積層構造
になつており、第１相と第２相とハロゲン組成を
異にするようなハロゲン局在乳剤（米国特許
3935014）、３価の金属イオンを含む酸性媒体中で
ハロゲン化銀粒子を生成させて異種金属を内蔵さ
せた乳剤（米国特許3447927号）などがある。こ
れらの内部潜像型乳剤は、本発明の実施に利用で
きる。本発明に用いられるアルカリ性現像液とは
現像薬のアルカリ水溶液である。
本発明に使用される現像薬は、ハロゲン化銀乳
剤用に従来使用されてきた現像薬から広く選択す
ることができる。即ち１・２−ないし１・４−ジ
ヒドロキシベンゼン、アスコルビン酸、レダクチ
ン酸及びそれらの誘導体、２−ないし、４−スル
フオンアミドフエノールとその誘導体、２−ない
し４−アミノフエノールとその誘導体、１・４−
フエニレンジアミンわけても米国特許2507154号
に記載されている誘導体、１−フエニル−３−ピ
ラゾリジノンとその誘導体、およびヒドロキシル
アミンとその誘導体が有利に使用される、その具
体例は前掲のJamesの著第11章に記されている。
これら現像薬は単独でも２つ以上を組合せて、特
に超加成性組合せで、使用してもよい。感光材料
中にバラスト基をもつ耐拡散化されたハイドロキ
ノン誘導体または色素放出レドツクス（DRR）
化合物のような不動化された還元剤が組込まれて
おり、現像薬がハロゲン化銀と不動化された還元
剤との間の電子移動剤として挙動するときには、
現像薬はｐ−メチルアミノフエノールのようなア
ミノフエノール類、１−フエニル４−メチル−４
−ヒドロキシメチル−３−ピラゾリジノン、１−
フエニル−４・４−ビス（ヒドロキシメチル）−
３−ピラゾリジノン、１−フエニル−４・４−ジ
メチル−３−ピラゾリジノンのようなピラゾリド
ン類もしくはＮ・Ｎ・N′・N′−テトラメチル−
ｐ−フエニレンジアミンのようなｐ−フエニレン
ジアミン類から選択されることが有利である。現
像薬は、現像液中、感光材料中、もしくは現像の
ときに感光材料に接触される第三の部材中のいず
れにも組込み得る。現像薬は前駆体の形で組込ま
れてもよい。現像液は水酸化ナトリウム、水酸化
カリウム、炭酸ナトリウム、リン酸ナトリウムの
ような塩基を含みPH10以上、好ましくは11.5以上
のアルカリ強度をもつ。現像液は亜硫酸ナトリウ
ム、アスコルビン酸塩、ピペリジノヘキソーズレ
ダクトンの如き酸化防止剤を含有し、臭化カリウ
ムのような銀イオン濃度調節剤を含有し得る。
一般式及び一般式で表わされる化合物中
で、本発明の実施に特に有利に使用されるもの
は、ピリジニウム環のメタ位（３−または５−
位）に電子吸引性置換基をもつ化合物中に見出さ
れる。例えばフツ素、塩素、臭素、沃素のような
ハロゲン原子；トリハロメチル基；シアノ基；
It should be understood that tautomers such as [Formula] are also included. The compound used in the present invention is mainly incorporated in a non-dissociated form with extremely low activity in light-sensitive materials under weakly acidic to neutral conditions, and changes to a dissociated form with high activity under alkaline development conditions, stabilizing the light-sensitive material. It is advantageous to select a compound that can maintain both properties and achieve activity under high reversal development conditions. Compounds having an active methylene group with acidity corresponding to a pKa value of generally 6.0 or more, preferably 7.0 or more, and preferably about 11 or less are useful, although it depends on factors such as the type of light-sensitive material and development conditions. Such adjustment of acidity can be achieved by appropriate selection of substituents R 1 and R 2 of the general formulas [] and []. The compound used in the present invention is clearly distinguished from the above-mentioned known heterocyclic quaternary ammonium salts in several respects. That is, in known compounds, the bond to the heterocyclic ammonium nitrogen atom is -CH 2 -
An alkylene group with 2 or more carbon atoms, represented by CH 2 -, is interposed between the two activating groups, and the presence of such an alkylene group constitutes an essential factor for its action as a nucleating agent. On the contrary, the compounds of the present invention have a structural difference in that they have a methylene group between the acyl group of the activating group, and the known 4
The difference in behavior is that the structural parts of the ammonium salts that are essential to their action are virtually unchanged between neutrality and alkalinity, whereas the compounds of the present invention dissociate in a manner closely related to their action. This clearly distinguishes the compounds of the invention from other known compounds. Further, the addition of a compound having a similar structure to the compound used in the present invention to the photographic layer is disclosed in West German patent application (OLS) No. 2448432, but the compound of the present invention is clearly not the same as the compound of this publication. distinguished. That is, the compound of the West German patent application, in particular 2-Bromo-1-, which is described as compound 8.
Phenacyl pyridinium bromide has a halogen atom at the 2-position of the pyridinium ring and reacts with gelatin, and does not exhibit a nucleation effect on internal latent image type silver halide emulsions during development. High maximum concentration (Dmax) according to the method of the invention
It is possible to obtain an inverted image that has both a low minimum density (Dmin) and a low minimum density (Dmin). This means that the silver halide contained in the light-sensitive material is converted into a silver image at a high rate, resulting in economical and resource-saving effects due to the reduction of the silver halide content in the light-sensitive material. By reducing the thickness of the emulsion layer, the effects of improving photographic performance such as improving image sharpness and shortening development processing time are realized. According to the method of the invention,
A desired photographic effect can be obtained with a small amount of nucleating agent, and therefore, the negative side effects such as staining caused by the use of a nucleating agent can be kept low. According to the method of the present invention, reversal development can be achieved in a short time. Appropriate selection of substituents can maintain a stable emulsion layer containing the necessary amount of nucleating agent to provide sufficient inversion density. According to the method of the present invention, during reversal image formation, there is no necessity for the formation of image unevenness due to the generation of gas such as nitrogen gas, which occurs with hydrazine compounds. In addition, by appropriate selection of substituents, the present invention uses compounds that can be easily synthesized in pure form and are easy to handle without the concerns of hygroscopicity and storage instability that occur with many quaternary salts. can do. Other features of the invention will be apparent from the detailed description and the examples. The internal latent image type silver halide emulsion used in the present invention mainly has photosensitive centers inside the silver halide emulsion grains, and a latent image is selectively formed thereon by exposure. The degree of latent image formation on the surface is low. Such an internal latent image type silver halide emulsion is developed by developing an image with a surface developer after exposure according to the description in James's book cited above, pp. 171-176. ) but
It is characterized by a distinctly lower amount of silver than the image obtained with the internal developer (corresponding to the total latent image). Internal latent image type silver halide emulsions can be made by various methods. For example, it has a high iodine content and is made by the ammonia process.
Burton's Emulsions (by EJWall, Photographic
Photographic Emulsions 35
~page 36, page 52-53 American Photographic
Publishing Co., (1929)) and U.S. Patent
2497875, 2563785), a large-grain primitive emulsion with a low iodine content made by the ammonia method (Old West German Patent Application (OLS) No. 2728108), and halogen Emulsions made by precipitation of silver chloride grains (US Pat. No. 3,511,662), first producing grains of a highly soluble silver salt such as silver chloride, then producing a grain of a less soluble silver salt such as (iod)silver bromide. A convergence emulsion by the castastrophe precipitation method (US Pat. No. 2,592,250), in which a chemically sensitized large-grain core emulsion is mixed with a fine-grain emulsion and then ripened to form a halogenated emulsion on the core grains. Core-shell emulsion coated with a silver shell (US Pat. No. 3,206,313)
(British Patent No. 1011062), a soluble silver salt solution and a soluble halide solution are simultaneously added to a chemically sensitized monodisperse core emulsion while keeping the silver ion concentration constant, thereby depositing silver halide on the core grains. A core-shell emulsion that coats a shell (UK Patent No. 1027146, US Patent No. 3761276), in which the emulsion grains have a laminated structure of two or more, and the halogen phase is such that the first phase and second phase have different halogen compositions. Emulsion (U.S. patent)
3935014), and an emulsion (US Pat. No. 3,447,927) in which silver halide grains are produced in an acidic medium containing trivalent metal ions to incorporate different metals. These internal latent image type emulsions can be utilized in the practice of this invention. The alkaline developer used in the present invention is an alkaline aqueous solution of a developer. The developer used in the present invention can be selected from a wide range of developers conventionally used for silver halide emulsions. Namely, 1,2- to 1,4-dihydroxybenzene, ascorbic acid, reductic acid and their derivatives, 2- to 4-sulfonamidophenol and its derivatives, 2- to 4-aminophenol and its derivatives, 1. 4-
Preference is given to using phenylenediamine, inter alia the derivatives described in US Pat. It is written in the chapter.
These developers may be used alone or in combinations of two or more, particularly in superadditive combinations. Diffusion-resistant hydroquinone derivatives or dye-releasing redoxes (DRR) with ballast groups in photosensitive materials
When an immobilized reducing agent such as a compound is incorporated and the developer behaves as an electron transfer agent between the silver halide and the immobilized reducing agent,
The developing agent is aminophenols such as p-methylaminophenol, 1-phenyl 4-methyl-4
-Hydroxymethyl-3-pyrazolidinone, 1-
Phenyl-4,4-bis(hydroxymethyl)-
Pyrazolidones such as 3-pyrazolidinone, 1-phenyl-4,4-dimethyl-3-pyrazolidinone, or N・N・N′・N′-tetramethyl-
Advantageously, it is selected from p-phenylene diamines such as p-phenylene diamine. The developer can be incorporated either in the developer solution, in the photosensitive material, or in a third member that contacts the photosensitive material during development. The developer may be incorporated in the form of a precursor. The developer contains a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium phosphate, and has an alkaline strength of PH 10 or higher, preferably 11.5 or higher. The developer solution contains antioxidants such as sodium sulfite, ascorbate, piperidinohexose reductone, and may contain silver ion concentration regulators such as potassium bromide. Among the compounds represented by the general formula and the general formula, those which are particularly advantageously used in the practice of the present invention are those at the meta position (3- or 5-
It is found in compounds that have an electron-withdrawing substituent at the For example, halogen atoms such as fluorine, chlorine, bromine, and iodine; trihalomethyl groups; cyano groups;
【式】で表わされるカルバモイル基（こ
こにR3とR4は夫々水素原子、アルキル基、アリ
ール基、もしくはヘテロ環基を表わす、これらア
ルキル基、アリール基もしくはヘテロ環基は炭素
原子数１から約20までをもち、さらに他の残基に
よつて置換されていてもよい。またR3とR4とは
チツ素原子とともに５員または６員の環を形成し
てもよい）；−COOR5で表わされるカルボン酸
エステル基（ここにR5はアルキル基、アリール
基、ヘテロ環基を表わす、これらアルキル基、ア
リール基、もしくはヘテロ環基は炭素原子数約20
までをもち、さらにハロゲン、アルキル基、アル
コキシ基、アリロキシ基、アシルアミノ基のよう
な他の残基によつて置換されていてもよい）；−
COR6で表わされるアシル基（ここにR6は水素原
子、ヒドロキシル基、アルキル基、アリール基、
もしくはヘテロ環基、アミノ基、アルコキシ基、
アリーロキシ基又は複素環オキシ基を表わす。こ
れらアルキル基、アリール基、ヘテロ環基は炭素
数約20までを含み、さらにハロゲン、アルキル
基、アルコキシ基、アリロキシ基、アシルアミノ
基のような他の残基によつて置換されていてもよ
い）；A carbamoyl group represented by the formula (where R 3 and R 4 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; these alkyl groups, aryl groups, or heterocyclic groups have a carbon atom number of 1 to -COOR _ A carboxylic acid ester group represented by 5 (herein, R 5 represents an alkyl group, an aryl group, or a heterocyclic group; each of these alkyl groups, aryl groups, or heterocyclic groups has approximately 20 carbon atoms)
and may be further substituted with other residues such as halogen, alkyl group, alkoxy group, allyloxy group, acylamino group);
Acyl group represented by COR 6 (where R 6 is a hydrogen atom, hydroxyl group, alkyl group, aryl group,
or a heterocyclic group, an amino group, an alkoxy group,
Represents an aryloxy group or a heterocyclic oxy group. These alkyl groups, aryl groups, and heterocyclic groups contain up to about 20 carbon atoms and may be further substituted with other residues such as halogen, alkyl groups, alkoxy groups, allyloxy groups, and acylamino groups.) ;
【式】で表わされるスルフアモイ
ル基；−SO2R6で表わされるスルフオニル基（R6
は上記と同義）；−NHCOR7で表わされるアシ
ルアミノ基（ここにR7はアルキル基、アリール
基、ヘテロ環基もしくはアミノ基を表わす、これ
らアルキル基、アリール基、ヘテロ環基、アルキ
ル基（例えばメチル基、エチル基、ブチル基、オ
クチル基、ドデシル基）及び／又はアリール基
（例えばフエニル基、トリル基、ナフチル基）に
よつて置換されてよいアミノ基は炭素原子数約20
を含み、さらに他の残基で置換されていてもよ
い）のような置換基をもつことが有利である。本
発明に特に有利な３位にカルボニル基ないしはシ
アノ基をもつピリジニウム環は、E.Klingsberg
編“Pyridine and its Derivatives”第３部、第
10章、特に第252〜263頁、272〜282頁（1962年、
Interscience Publishers刊）に記載されている３
−置換pridineから誘導されるピリジニウムから
選ぶことができる。一般式で表わさる化合物中
で表わされる化合物中で本発明の実施に特に有利
に使用できるものは、R2がアリール基もしくは
芳香族性をもつヘテロ環基である化合物中に見出
される、例えばフエニル、ナフチル、チエニル、
などである。このうちフエニル基もしくは置換さ
れたフエニル基が合成の見地から優れている。フ
エニル基の置換基としてはフツ素、塩素、臭素の
ようなハロゲン原子；メチル、エチル、プロピ
ル、ｔ−ブチル、ｔ−アミル、オクチルのような
炭素原子数１から約20までのアルキル基；メトオ
キシ、エトキシ、イソプロポキシ、ベンジルオキ
シ、オクチルオキシ、ドデシルオキシ、ヘキサデ
シルオキシのような炭素原子数１から約20までの
アルコキシ基；フエニルオキシ、３−ペンタデシ
ルフエニルオキシのような炭素原子数６から約25
までのアリールオキシ基；−NHCOR8または−
NHSO2R8で表わされるアシルアミノ基（ここに
R8はアルキル基、アリール基、ヘテロ環もしく
はアミノ基を表わす、これはアルキル基、アリー
ル基、ヘテロ環基、アミノ基は炭素原子数約20ま
でを含み、さらに他の残基で置換されていてもよ
い）が有利である。R8で表わされる、アルキル
基は炭素原子数１〜約20で、例えばメチル基、エ
チル基、ブチル基、オクチル基、ドデシル基な
ど；アリール基は炭素原子数６〜約20で例えばフ
エニル基、トリル基、ナフチル基など；アミノ基
は置換基例えばアルキル基（例えばメチル基、エ
チル基、ブチル基、オクチル基、ドデシル基な
ど）、アリール基（例えばフエニル基、トリル
基、ナフチル基など）などによつて置換されてい
てよい。
一般式とのX-で表わされるアニオンは広
い範囲から選ぶことができる。対イオンとしての
アニオンは、発明の実施のときに写真層または処
理組成物中の他のアニオンと容易に交換される点
と現像処理条件ではアニオンは機能種であるイリ
ドから離脱する点とから、アニオン種は写真的に
不利な作用がない限り限定されないことは容易に
理解できよう。本発明の説明にはアニオンとし
て、専ら塩素、臭素、ヨウ素があげられている
が、これは化合物の合成の便宜のためであつて、
硝酸イオン、硫酸イオン、過塩素酸イオン等の無
機アニオン、並びに脂肪酸イオン、トルエンスル
フオン酸イオン、メタンスルフオン酸イオン、ピ
クリン酸イオン等の有機アニオンも同じように用
いることができる。
本発明に有利に使用できる化合物の具体的な例
をあげれば下のようなものがある。
本発明に用いられるピリジニウム・イリドを与
えるβ−ケトピリジニウム塩は公知化合物であ
り、よく知られた方法で合成することができる。
即ちF.Kro¨hnkeの報告（Chem.Ber.、68、1177−
95（1935））に記載されているようにα−ハロケ
トン（α−haloketone）をピリジン類に作用させ
る方法、L.C.Kingの報告（J.A.C.S.（ジヤーナ
ル オブ ザ アメリカン ケミカル ソサイエ
テイ（Journal of the American Chemical
Society）の略）66、894−５（1944））に記載さ
れているようにケトンとピリジン類とに沃素を作
用させる方法並びにL.C.King等の報告、J.A.C.
S.70、4154−５（1948）、に記載されているよう
にピリジンにジアゾケトンを作用させる方法など
がある。ピリジニウムのアニオンはハロゲン化物
に、過塩素酸のような遊離酸の過剰量を作用させ
るとか硝酸銀のような可溶性銀塩の当量を作用さ
せる、ないしはイオン交換樹脂を使用する等の方
法、炭酸ナトリウムによつてイリドとして析出分
離し次いで酸によつて中和する方法によつて他の
アニオンに変換できる。本発明に有利に使用でき
るβ−ケトピリジニウム塩のいくつかの合成方法
は、上記の文献の他に前記のW.G.Phillipsらの文
献、J.L.Hartwell等の文献（J.A.C.S.68、868−
70（1946））、L.C.King等の文献（J.A.C.S.70、
239−40（1948））、並びにI.Zugravescu等の成書
“Ｎ−Ylid Chemistry”（Mc Graw Hill版
（1976））に記載されている。
本発明においては、ピリジニウム・イリドを与
えるβ−ケトピリジニウム塩を直接に乳剤層に組
んでもよく、また低分子量のもの、もしくはバラ
スト茎をもたないもののような移動性のβ−ケト
ピリジニウム塩は乳剤層に近接する親水性コロイ
ド層に組込んでもよい。さらに現像のときに接触
する他の要素、例えば拡散転写フイルムユニツト
の展開シート、中に組込んでもよい。ピリジニウ
ムイリドを与えるβ−ケトピリジニウム塩の使用
量は、乳剤の型、性質並びに処理液組成などによ
つて大きく変化するが、一般にハロゲン化銀１モ
ル当り１×10-4モルから６×10-3モルまでの量が
用でき、３×10-4モルから３×10-3モルまでの量
が有利である。
本発明は、内部潜像型ハロゲン化銀乳剤の直接
反転現像を有利にする他の化合物との併用によつ
て、さらに有利に実施することができる。例えば
米国特許2497917号に記載されているトリアゾー
ル化合物、米国特許3352672号に記載されている
ようなテトラゾール化合物に共存によつて低い
Dminと高いDmaxとを同時に得ることが容易に
なる。英国特許1151363号、1187029号、と
1195837号に記載されているようなヨードイオン
供与体は高いDmaxを与えることを助ける。この
他に鎖状ないし環状のチオ尿素誘導体のごとき活
性硫黄化合物または前駆体は、特に低温度におけ
る反転現像を促進することができる。本発明にお
いては、ピリジニウム・イリドを与えるβ−ケト
ピリジニウム化合物の他に、ヒドラジド化合物、
または４級アンモニウム化合物のような従来知ら
れていた核形成剤をも併せて使用することができ
る。この他にテトラメチルハイドロキノン、テト
ラメトキシハイドロキノン、ｔ−オクチルハイド
ロキノン、２−sec−オクタデシル−５−スルホ
ハイドロキノン、２−Ｎ−モルホリル−５−ｔ−
オクチルハイドロキノン等のハイドロキノン類ま
たはこれらのｏ−アシル化体またはオキジン、ビ
スオキジン類のような先駆体を現像のときに共存
させると造核作用が促進される。
本発明によつて得られる画像は、現像銀による
白黒写真像として、ハロゲン化銀による酸化によ
つて形成されるカラー画像として利用される。カ
ラー画像の形成には各種の色素像供与化合物が利
用できるが、わけても１級アミノ現像薬とカプラ
ーとの組合せ、現像における酸化の結果として拡
散性色素を放出する色素レリーサー（DRR化合
物）等が特に有用である。
本発明の実施のために使用されるカプラーとし
ては、前掲のT.H.Jamesの著書第12章（特に353
〜361頁）に記載されているようなフエノール性
の活性水素をもつ化合物及び活性メチレン基をも
つ化合物、例えばフエノール類、ナフトール類、
ピラゾロン類、アシルアセトアニリド類、ベンツ
イソオキサゾロン類、ピラゾロベンツイミダゾー
ル類、ピラゾロトリアゾール類、インダゾロン類
等が使用できる。これらのカプラーは炭素数８以
上のアルキル基もしくはアルキルアリール基など
の疎水性基を耐拡散化基（バラスト基）としても
つことが有利であり、反応位置の水素原子の一つ
がカラー現像薬の酸化生成物によつて離脱される
残基によつて置換されていることが有利である。
本発明においては、拡散転写によりカラー画像
を得るために種々の色素供与体が直接反転乳剤と
組合せて使用される。分子内に上記のような耐拡
散化基をもち、酸化された現像薬と反応すること
によつて拡散性色素を放出するような化合物が特
に有利である。このような化合物にはｐ−フエニ
レンジアミン系現像薬とともに使用するのに適し
たDDRカプラー（米国特許3227550）、特公昭48
−39165に記載されているようなアミドラゾン化
合物、特公昭48−32129に述べられているような
酸化閉環によつて色素を放出する化合物、米国特
許3928312号、3993638号、米国特許4055428号、
ドイツ特許公開2645656号、に記されているよう
な酸化開裂を受けて色素を放出するようなDRR
化合物等があげられる。このような色素像を与え
る直接反転乳剤は、謂ゆるピールアパート型及び
一体型の拡散転写フイルムユニツトに組込むこと
ができる。
本発明に使用する感材材料は各種の支持体をも
つことができる、例えばガラス、紙、並びにポリ
アクリル酸エステル、ポリスチレン、ポリカーボ
ネート、ポリエチレンテレフタレート、酢酸セル
ローズのようなフイルムベース等がある。
実施例 １
透明な三酢酸セルローズ・フイルムベース上
に、第一層としてマゼンタ色素放出レドツクス化
合物（M1）0.64ｇ／m2、Ｎ・Ｎ−ジエチルラウ
リルアミド0.2ｇ／m2とゼラチン1.3ｇ／m2を含む
層を塗布し、その上に、粒子径が約１・３ミクロ
ン正八面体をなす臭化銀60ミリモルとゼラチン
5.5ｇを含む内部潜像型ハロゲン化銀乳剤100ｇに
色増感剤S1とS2の溶液、後記の核形成剤の溶液と
２−スルホ−５−ｎ−ペンタデシルハイドロキノ
ン・カリウム塩（0.023モル／モルAg）を順次に
添加して完成させた乳剤を塗布量が1.55ｇAg／
m2になるように第２層として塗布した。さらにこ
の上に２・５−ジ−ｔ−ドデシルハイドロキノン
0.2ｇ／m2とゼラチン1.3ｇ／m2を含む保護層とし
て塗布して感光要素を完成させた。
一方、透明なポリエチレンテレフタレート・フ
イルムベース上に、ポリー（３−または４−トリ
−ｎ−ヘキシルアンモニウムメチル）スチレン塩
化物3.0ｇ／m2とゼラチン3.0ｇ／m2とを含む媒染
層を塗布して受像要素を作つた。
感光要素にセンシメトリー用の段階的露光を与
えた後に、感光要素と受像要素を向い合せて、両
要素の間に液厚が80ミクロンになるように処理液
を展開し、25℃で３分間後に受像層を剥離し、１
％酢酸浴中で中和した後に５分間水洗し、次いで
乾燥させたところマゼンタ色のポジ画像を得た。
残つた感光要素をチオ硫酸ナトリウム溶液で定着
し、水洗し乾燥させたところ、銀のポジ像と残存
の色材のネガ像の重なりを得た。
このとき感光要素は、４・６−ジクロロ−２−
ヒドロキシ−ｓ−トリアジンのナトリウム塩によ
つて、受像要素はホルムアルデヒドでそれぞれ硬
膜してあつた。
処理液は下記の組成をもつていた。
カルボキシメチルセルローズ・ナトリウム塩
……60ｇ
酸性亜硫酸ナトリウム ……1.0ｇ
５−メチルベンゾトリアゾール ……3.5ｇ
４−メチル−４−ヒドロキメチル−１−フエニル
−３−ピラゾリジノン ……13ｇ
メチルハイドロキノン ……0.2ｇ
水酸化カリウム ……56ｇ
水 ……710c.c.
受像要素を濃度測定して、下記のような結果
（図１及び図２参照）を得た。
使用した色素放出レドツクス化合物は下記の構
造をもつていた。
使用した色増感剤は下記の構造をもつていた。
臭化フエナシル17.5ｇをアセトン16mlに溶解
し、ニコチンアミド10.73ｇをアルコール24mlに
とかした熱溶液と合し、５分間スチームバス上で
加熱する。冷却後結晶を取し、アルコールとベ
ンゼンで洗滌し、淡黄色の結晶（３−カルバモイ
ル−１−フエナシル−ピリジニウム・臭化物）
15.5ｇを得た。元素分析値C52.1％、H4.2％、
N8.8％、Br3.10ミリモル／ｇ（C14H13O2N2Brに
対する計算値C52.4％、H4.1％、N8.7％、Br3.11
ミリモル／ｇ）。
上記の３−カルバモイル−１−フエナシル−ピ
リジニウム・臭化物を水に溶解し0.803％
（0.025M）の溶液を調製した。比較のために米国
特許3227552号に記載のフオルミル−ｐ−トリル
ヒドラジンSulfamoyl group represented by [Formula]; Sulfonyl group represented by -SO 2 R 6 (R 6
is the same as above); an acylamino group represented by -NHCOR 7 (where R 7 represents an alkyl group, an aryl group, a heterocyclic group, or an amino group; The amino group, which may be substituted by a methyl group, ethyl group, butyl group, octyl group, dodecyl group) and/or an aryl group (e.g. phenyl group, tolyl group, naphthyl group), has about 20 carbon atoms.
It is advantageous to have substituents such as , which may be further substituted with other residues. A pyridinium ring having a carbonyl group or a cyano group at the 3-position which is particularly advantageous for the present invention is E. Klingsberg
ed. “Pyridine and its Derivatives” Part 3, Vol.
Chapter 10, especially pp. 252-263, 272-282 (1962,
3 listed in Interscience Publishers)
- Pyridinium derived from substituted pridine. Among the compounds represented by the general formula, those which can be particularly advantageously used in the practice of the present invention are found in compounds in which R 2 is an aryl group or a heterocyclic group having aromatic properties, such as phenyl , naphthyl, thienyl,
etc. Among these, phenyl groups or substituted phenyl groups are superior from the viewpoint of synthesis. Substituents for the phenyl group include halogen atoms such as fluorine, chlorine, and bromine; alkyl groups having from 1 to about 20 carbon atoms such as methyl, ethyl, propyl, t-butyl, t-amyl, and octyl; methoxy , ethoxy, isopropoxy, benzyloxy, octyloxy, dodecyloxy, hexadecyloxy, from 1 to about 20 carbon atoms; from 6 to about 20 carbon atoms, such as phenyloxy, 3-pentadecyl phenyloxy; about 25
Aryloxy group up to; -NHCOR 8 or -
Acylamino group represented by NHSO 2 R 8 (here
R 8 represents an alkyl group, an aryl group, a heterocyclic group, or an amino group, where the alkyl group, aryl group, heterocyclic group, or amino group contains up to about 20 carbon atoms and is further substituted with other residues. ) is advantageous. The alkyl group represented by R 8 has 1 to about 20 carbon atoms, such as methyl, ethyl, butyl, octyl, dodecyl, etc.; the aryl group has 6 to about 20 carbon atoms, such as phenyl, Tolyl group, naphthyl group, etc.; Amino group can be used as a substituent such as alkyl group (e.g. methyl group, ethyl group, butyl group, octyl group, dodecyl group, etc.), aryl group (e.g. phenyl group, tolyl group, naphthyl group, etc.) Therefore, it may be replaced. The anion represented by X - with the general formula can be selected from a wide range. The anion as a counter ion is easily exchanged with other anions in the photographic layer or processing composition during the practice of the invention, and the anion separates from the functional species ylide under processing conditions. It will be readily understood that the anion species are not limited as long as they do not have adverse photographic effects. In the description of the present invention, chlorine, bromine, and iodine are exclusively mentioned as anions, but this is for the convenience of compound synthesis.
Inorganic anions such as nitrate ion, sulfate ion, perchlorate ion, etc., as well as organic anions such as fatty acid ion, toluenesulfonate ion, methanesulfonate ion, picrate ion, etc. can be similarly used. Specific examples of compounds that can be advantageously used in the present invention include the following. The β-ketopyridinium salt that provides the pyridinium ylide used in the present invention is a known compound and can be synthesized by a well-known method.
Namely, the report of F. Kro¨hnke (Chem. Ber., 68 , 1177-
95 (1935)), the LCKing report (JACS (Journal of the American Chemical Society)
(Society) 66 , 894-5 (1944)), a method of acting iodine on ketones and pyridines, and reports on LCKing, etc., JAC
S. 70 , 4154-5 (1948), there is a method of reacting diazoketone with pyridine. The pyridinium anion can be obtained by treating the halide with an excess of a free acid such as perchloric acid, with an equivalent amount of a soluble silver salt such as silver nitrate, or by using an ion exchange resin, or with sodium carbonate. Therefore, it can be converted into other anions by precipitating and separating it as a ylide and then neutralizing it with an acid. Some synthetic methods of β-ketopyridinium salts that can be advantageously used in the present invention are described in addition to the above-mentioned documents, such as the above-mentioned document by WG Phillips et al. and JL Hartwell et al. (JACS 68 , 868-
70 (1946)), LCKing et al. (JACS 70 ,
239-40 (1948)) and in the book "N-Ylid Chemistry" by I. Zugravescu et al. (Mc Graw Hill edition (1976)). In the present invention, β-ketopyridinium salts providing pyridinium ylide may be incorporated directly into the emulsion layer, and mobile β-ketopyridinium salts such as those with low molecular weight or those without ballast stems may be used. It may also be incorporated into a hydrophilic colloid layer adjacent to the emulsion layer. Furthermore, it may be incorporated into other elements that come into contact during development, such as a spreading sheet of a diffusion transfer film unit. The amount of β-ketopyridinium salt used to give pyridinium ylide varies greatly depending on the type and properties of the emulsion, the composition of the processing solution, etc., but is generally from 1 x 10 -4 mol to 6 x 10 -4 mol per mol of silver halide . Amounts of up to 3 mol can be used, amounts of 3×10 -4 mol to 3×10 -3 mol being advantageous. The present invention can be carried out more advantageously in combination with other compounds that facilitate direct reversal development of internal latent image type silver halide emulsions. For example, triazole compounds as described in US Pat. No. 2,497,917 and tetrazole compounds as described in US Pat. No. 3,352,672 have low
It becomes easy to obtain Dmin and high Dmax at the same time. British patents 1151363, 1187029, and
Iodide ion donors such as those described in US Pat. No. 1,195,837 help provide high Dmax. In addition, active sulfur compounds or precursors such as linear or cyclic thiourea derivatives can promote reversal development, especially at low temperatures. In the present invention, in addition to the β-ketopyridinium compound giving pyridinium ylide, hydrazide compounds,
Alternatively, a conventionally known nucleating agent such as a quaternary ammonium compound can also be used. In addition, tetramethylhydroquinone, tetramethoxyhydroquinone, t-octylhydroquinone, 2-sec-octadecyl-5-sulfohydroquinone, 2-N-morpholyl-5-t-
When hydroquinones such as octylhydroquinone, o-acylated products thereof, or precursors such as oxidine and bisuoxidine are present during development, the nucleation effect is promoted. The images obtained by the present invention can be used as black and white photographic images using developed silver, or as color images formed by oxidation using silver halide. A variety of dye image-providing compounds are available for forming color images, particularly combinations of primary amino developers and couplers, and dye releasers (DRR compounds) that release diffusible dyes as a result of oxidation during development. Useful. Couplers used in the practice of the present invention include chapter 12 of the above-mentioned book by TH James (particularly 353
Compounds with phenolic active hydrogen and compounds with active methylene groups, such as phenols, naphthols, as described in
Pyrazolones, acylacetanilides, benzisoxazolones, pyrazolobenzimidazoles, pyrazolotriazoles, indazolones, etc. can be used. It is advantageous for these couplers to have a hydrophobic group such as an alkyl group or an alkylaryl group having 8 or more carbon atoms as a diffusion-resistant group (ballast group), and one of the hydrogen atoms at the reaction site is resistant to oxidation of the color developer. Advantageously, it is replaced by a residue which is removed by the product. In the present invention, various dye-donors are used in combination with direct reversal emulsions to obtain color images by diffusion transfer. Particularly advantageous are compounds which have the above-mentioned diffusion-resistant groups in their molecules and which release a diffusible dye upon reaction with an oxidized developer. Such compounds include DDR couplers suitable for use with p-phenylenediamine developers (U.S. Pat. No. 3,227,550);
Amidrazone compounds as described in Japanese Patent Publication No. 39165, compounds that release dyes by oxidative ring closure as described in Japanese Patent Publication No. 48-32129, US Pat. No. 3928312, US Pat. No. 3993638, US Pat.
A DRR that releases a dye upon oxidative cleavage as described in German Patent Publication No. 2645656.
Examples include compounds. Direct reversal emulsions that provide such dye images can be incorporated into so-called peel-apart and integral diffusion transfer film units. The sensitive material used in the present invention can have various supports, such as glass, paper, and film bases such as polyacrylic acid ester, polystyrene, polycarbonate, polyethylene terephthalate, and cellulose acetate. Example 1 On a transparent cellulose triacetic acid film base, as a first layer 0.64 g/m 2 of magenta dye-releasing redox compound (M 1 ), 0.2 g/m 2 of N·N-diethyl laurylamide and 1.3 g/m 2 of gelatin. A layer containing m 2 is coated, and on top of that, 60 mmol of silver bromide with a regular octahedral particle size of about 1.3 microns and gelatin are applied.
100 g of an internal latent image type silver halide emulsion containing 5.5 g, a solution of color sensitizers S 1 and S 2 , a solution of the nucleating agent described below and 2-sulfo-5-n-pentadecylhydroquinone potassium salt (0.023 The coating amount of the emulsion was 1.55gAg/mol/molAg) was added sequentially.
It was applied as a second layer in an amount of m 2 . Furthermore, 2,5-di-t-dodecylhydroquinone
The photosensitive element was completed by coating as a protective layer containing 0.2 g/m 2 and gelatin 1.3 g/m 2 . Meanwhile, a mordant layer containing 3.0 g/m 2 of poly(3- or 4-tri-n-hexylammonium methyl) styrene chloride and 3.0 g/m 2 of gelatin was coated on a transparent polyethylene terephthalate film base. I created an image receiving element. After giving the photosensitive element a stepwise exposure for sensimetry, the photosensitive element and the image receiving element were placed facing each other, and the processing solution was spread between the two elements to a thickness of 80 microns, and then heated at 25°C for 3 minutes. After that, the image-receiving layer is peeled off and 1
% acetic acid bath, washed with water for 5 minutes, and then dried to obtain a magenta positive image.
The remaining photosensitive element was fixed with a sodium thiosulfate solution, washed with water, and dried to yield a superimposed positive silver image and negative image of the remaining colorant. At this time, the photosensitive element is 4,6-dichloro-2-
The receiving elements were each formaldehyde hardened with the sodium salt of hydroxy-s-triazine. The treatment liquid had the following composition. Carboxymethyl cellulose sodium salt
...60g Sodium acid sulfite ...1.0g 5-methylbenzotriazole ...3.5g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidinone ...13g Methylhydroquinone ...0.2g Potassium hydroxide ...56g Water...710c.c. The concentration of the image receiving element was measured and the following results were obtained (see Figures 1 and 2). The dye-releasing redox compound used had the following structure. The color sensitizer used had the following structure. 17.5 g of phenacyl bromide are dissolved in 16 ml of acetone, combined with a hot solution of 10.73 g of nicotinamide in 24 ml of alcohol and heated on a steam bath for 5 minutes. After cooling, collect the crystals and wash with alcohol and benzene to obtain pale yellow crystals (3-carbamoyl-1-phenacyl-pyridinium bromide).
15.5g was obtained. Elemental analysis value C52.1%, H4.2%,
N8.8%, Br3.10 mmol /g (calculated value for C14H13O2N2Br C52.4 % , H4.1%, N8.7 %, Br3.11
mmol/g). Dissolve the above 3-carbamoyl-1-phenacyl-pyridinium bromide in water to 0.803%
(0.025M) solution was prepared. For comparison, formyl-p-tolylhydrazine as described in U.S. Pat. No. 3,227,552
【式】をメ
タノールに溶解し1.662％（0.10M）の溶液と米
国特許3734738号に記載の１−（２−フオルミルエ
チル）−２−メチル・ベンゾチアゾリウム臭化物
A 1.662% (0.10M) solution of [Formula] in methanol and 1-(2-formylethyl)-2-methyl benzothiazolium bromide described in U.S. Pat. No. 3,734,738.
【式】をメタノールに溶
解し1.43％（0.050M）の溶液を調製した。
第１図及び第２図は新規な核形成剤（化合物
54）によつて形成される反転画像の特性を、公知
の核形成剤との比較で示したものである。
第２図の縦軸に受像要素中のポジ転写像の濃度
値（透過濃度）を、第１図の縦軸に感光要素中の
現像銀の量の値（μｇ／cm2）を、それぞれ露光量
（横軸は露光量の対数）に対して示してある。各
曲線と核形成剤の種類との関係は下表に示した。
これらの結果から、本発明の核形成剤は公知の化
合物と比較して少い添加量で高い最大濃度と低い
最小濃度とを同時に与えることができ過大な露光
量においてネガ像（逆転像）を与える傾向が少い
という優れた点をもつことが明らかにされた。[Formula] was dissolved in methanol to prepare a 1.43% (0.050M) solution. Figures 1 and 2 show novel nucleating agents (compounds).
54) is shown in comparison with known nucleating agents. The vertical axis in Figure 2 represents the density value (transmission density) of the positive transfer image in the image-receiving element, and the vertical axis in Figure 1 represents the amount of developed silver (μg/cm 2 ) in the photosensitive element after exposure. It is shown in relation to the amount (the horizontal axis is the logarithm of the exposure amount). The relationship between each curve and the type of nucleating agent is shown in the table below.
From these results, the nucleating agent of the present invention can provide a high maximum density and a low minimum density at the same time with a small addition amount compared to known compounds, and can produce negative images (reverse images) at excessive exposure doses. It was revealed that it has the advantage of having a small tendency to give.
【表】
実施例 ２
実施例１と同じ条件で、核形成剤を変えて感光
要素を作製した。同条件で現像処理して表１の如
き結果を得た。
これらの結果は、適切な置換基の選択によつて
良好な特性をもつた反転像が得られることを示し
ている。
これに反して、下記に例示されているような化
合物は見るべき反転像を示さなかつた。
[Table] Example 2 Photosensitive elements were produced under the same conditions as in Example 1 but with different nucleating agents. The results shown in Table 1 were obtained by developing under the same conditions. These results indicate that a reversal image with good properties can be obtained by selecting appropriate substituents. In contrast, compounds such as those exemplified below showed no appreciable reversal image.
【表】【table】
【表】
実施例 ３
透明なポリエチレンテレフタレート・フイルム
ベースに、第一層としてポリ（３−または４−ト
リ−ｎ−ヘキシルアンモニウムメチル）スチレン
塩化物3.0ｇ／m2とゼラチン2.5ｇ／m2とを含む媒
染層を、第２層としてチタンホワイト20ｇ／m2と
ゼラチン2.5ｇ／m2とを含む光反射層を、第３層
としてカーボンブラツク3.0／m2とゼラチン2.0
ｇ／m2とを含む遮光層を塗布してなる塗布物の上
に、下記の層を順次に塗布して拡散転写用感光要
素を作つた。
第４層：シアン色素放出レドツクス化合物0.56
ｇ／m2とゼラチン1.5ｇ／m2とを含む層。
第５層：赤感性の内部潜像型ハロゲン化銀乳剤に
前記核形成剤・化合物54のメチルアルコール溶
液1.0×10-3モル／モル銀、２−スルホ−５−
ｎ−ペンタデシルハイドロキノン・カリウム塩
のメタノール溶液と４−ヒドロキシ−６−メチ
ル−１・３・3a・７テトラアザインデン・ナト
リウム塩の水溶液を順次に添加して調製した液
を、1.5ｇAg／m2とゼラチン1.5ｇ／m2になるよ
うに塗布した赤感性乳剤層。
第６層：２・５−ジ−ｔ−ペンタデシルハイドロ
キノン0.8ｇ／m2とゼラチン1.3ｇ／m2とを含む
中間層。
第７層：マゼンタ色素放出レドツクス化合物0.65
ｇ／m2とゼラチン1.2ｇ／m2とを含む層。
第８層：緑感性の内部潜像型ハロゲン化銀乳剤に
前記核形成剤・化合物54 1.0×10-3モル／モル
銀のメチルアルコール溶液、２−スルホ−５−
ｎ−ペンタデシルハイドロキノン・カリウム塩
のメタノール溶液と４−ヒドロキシ−６−メチ
ル−１・３・3a・７−テトラアザインデン・ナ
トリウム塩の水溶液を順次に添加して調製した
液を、1.35ｇAg／m2とゼラチン1.4ｇ／m2にな
るように塗布した緑感性乳剤層。
第９層：２・５−ジ−ｔ−ペンタデシルハイドロ
キノン0.8ｇ／m2とゼラチン1.3ｇ／m2とを含む
中間層。
第10層：黄色色素放出レドツクス化合物0.75ｇ／
m2とゼラチン1.4ｇ／m2とを含む層。
第11層：青感性の内部潜像型ハロゲン化銀乳剤に
核形成剤１−〔４−（２−フオルミルヒドラジ
ノ）フエニル〕−３−フエニルチオ尿素のメタ
ノール溶液、２−スルホ−５−ｎ−ペンタデシ
ルハイドロキノン・カリウム塩のメタノール溶
液と４−ヒドロキシ−６−メチル−１・３・
3a・７−テトラアザインデン・ナトリウム塩の
水溶液を順次に添加して調製した液を、1.5ｇ
Ag／m2とゼラチン1.5ｇ／m2になるように塗布
した青感性乳剤層。
第12層：２・５−ジ−ｔ−ペンタデシルハイドロ
キノン0.10ｇ／m2とゼラチン1.3ｇ／m2とを含
む保護層。
これらの層は１・３−ビス（ビニルスルフオニ
ル）−２−プロパノールを用いて硬膜してあつ
た。
ここに用いた色素放出レドツクスは下記の通り
である。
ここに用いた色増感剤は下記の通りである：
赤感性
緑感性：実施例１に用いたものと同じ一対の増感
剤
青感性
一方透明なポリエチレンテレフタレート・フイ
ルムベース上に、第１層としてポリアクリル酸17
ｇ／m2、Ｎ−ヒドロキシサクシンイミドベンゼン
スルフオネート0.06ｇ／m2とエチレングリコール
0.5ｇ／m2と含む厚さ７ミクロンに塗布した中和
層、第２層として酢酸セルローズ（酢化度54）、
を厚さ２ミクロンに塗布したタイミング層と第３
層として塩化ビニリデンとアクリル酸との共重合
ラテツクスを厚さ４ミクロンに塗布したタイミン
グ層をもつ展開シートを用意した。
感光要素にセンシトメトリー用の段階的色分解
露光を与えた後に、感光要素と展開シートとを向
い合せて両者の間に液厚が80ミクロンになるよう
に25℃において処理液を展開したところ、色分解
されたポジ画像が次第に形成されるのが観察され
た。処理後１時間目に灰色スケール部分の濃度を
測定して表２の結果を得た。[Table] Example 3 A transparent polyethylene terephthalate film base with 3.0 g/m 2 of poly(3- or 4-tri-n-hexylammonium methyl) styrene chloride and 2.5 g/m 2 of gelatin as the first layer. The second layer is a light reflective layer containing 20 g/m 2 of titanium white and 2.5 g/m 2 of gelatin, and the third layer is carbon black 3.0/m 2 and 2.0 g/m 2 of gelatin.
A light-sensitive element for diffusion transfer was prepared by sequentially coating the following layers on a coated product formed by coating a light-shielding layer containing 2 g/m 2 . 4th layer: cyan dye releasing redox compound 0.56
g/m 2 and gelatin 1.5 g/m 2 . Fifth layer: Red-sensitive internal latent image type silver halide emulsion with 1.0 x 10 -3 mol/mol silver, 2-sulfo-5- methyl alcohol solution of the nucleating agent/Compound 54
A solution prepared by sequentially adding a methanol solution of potassium salt of n-pentadecylhydroquinone and an aqueous solution of sodium salt of 4-hydroxy-6-methyl-1,3,3a,7tetraazaindene was added at 1.5 g/m 2 and a red-sensitive emulsion layer coated with gelatin at a concentration of 1.5 g/m 2 . Sixth layer: Intermediate layer containing 0.8 g/m 2 of 2,5-di-t-pentadecylhydroquinone and 1.3 g/m 2 of gelatin. 7th layer: Magenta dye-releasing redox compound 0.65
g/m 2 and gelatin 1.2 g/m 2 . 8th layer: A green-sensitive internal latent image type silver halide emulsion containing the above-mentioned nucleating agent/compound 54 in a methyl alcohol solution of 1.0×10 -3 mol/mol silver, 2-sulfo-5-
A solution prepared by sequentially adding a methanol solution of potassium salt of n-pentadecylhydroquinone and an aqueous solution of sodium salt of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added to the solution at 1.35gAg/ m 2 and gelatin 1.4 g/m 2 in a green-sensitive emulsion layer. Ninth layer: Intermediate layer containing 0.8 g/m 2 of 2,5-di-t-pentadecylhydroquinone and 1.3 g/m 2 of gelatin. 10th layer: Yellow dye-releasing redox compound 0.75g/
m 2 and 1.4 g/m 2 of gelatin. Eleventh layer: Blue-sensitive internal latent image type silver halide emulsion with nucleating agents 1-[4-(2-formylhydrazino)phenyl]-3-phenylthiourea in methanol solution, 2-sulfo-5- Methanol solution of n-pentadecylhydroquinone potassium salt and 4-hydroxy-6-methyl-1.3.
1.5 g of a solution prepared by sequentially adding an aqueous solution of 3a.7-tetraazaindene sodium salt.
Blue-sensitive emulsion layer coated at Ag/m 2 and gelatin 1.5 g/m 2 . 12th layer: protective layer containing 0.10 g/m 2 of 2,5-di-t-pentadecylhydroquinone and 1.3 g/m 2 of gelatin. These layers were hardened using 1,3-bis(vinylsulfonyl)-2-propanol. The dye-releasing redox used here is as follows. The color sensitizers used here are as follows: Red sensitivity Green Sensitivity: Same pair of sensitizers as used in Example 1 Blue Sensitivity On the other hand, polyacrylic acid 17 was used as the first layer on a transparent polyethylene terephthalate film base.
g/m 2 , N-hydroxysuccinimidebenzenesulfonate 0.06 g/m 2 and ethylene glycol
Neutralization layer coated to a thickness of 7 microns containing 0.5 g/ m2 , cellulose acetate (acetate degree 54) as the second layer,
A timing layer with a thickness of 2 microns and a third
A spread sheet having a timing layer coated with a copolymer latex of vinylidene chloride and acrylic acid to a thickness of 4 microns was prepared. After applying stepwise color separation exposure to the photosensitive element for sensitometry, the photosensitive element and the developing sheet were placed facing each other and the processing solution was developed at 25°C so that the liquid thickness was 80 microns between the two. , a color-separated positive image was observed to gradually form. One hour after treatment, the density of the gray scale area was measured and the results shown in Table 2 were obtained.
【表】
ここで使用した処理液の組成は、実施例１の処
理液にさらにカーボンブラツク150ｇを添加、分
散させたものであつた。
本実施例に使用した化合物54は下記のようにし
て合成された。
(1) Ｎ−ヘキサデシルニコチンアミド
セチルアミン30.7ｇとピリジン33.2ｇをアセ
トニトリル200mlに分散し、水冷下ニコチン酸
クロリド塩酸塩25ｇを添加する。さらに55℃に
て３時間反応させた後、水800mlを加えて生成
した結晶を取する。エタノール500mlより再
結晶すると目的物が36.3ｇが得られた。融点85
−７℃。元素分析結果C76.1％、H11.1％、
N8.0％（C22H38N2Oに対する計算値はC76.3
％、H11.1％、N8.1％）。
(2) ３−Ｎ−ヘキサデシルカルバモイル−１−フ
エナシルピリジニウムブロミド（化合物54）
Ｎ−ヘキサデシルニコチンアミド10.4ｇとフ
エナシルブロミド6.0ｇとをベンゼン100ml中80
℃で７時間反応させる。放冷すると結晶が析出
するからさらにヘキサン100mlを加えて晶析さ
せた後、目的物を取する。収量15.4ｇ。融点
110〜127℃（流れる温度）。元素分析結果
C65.7％、H8.4％、N5.3％（C30H45BrN2O2に対
する計算値はC66.0％、H8.3％、N5.1％）。
本発明の好ましい具体的な実施態様をあげれば
以下の通りである。
(1) 下記の一般式で表わされる化合物と組合わさ
れた、内部潜像型ハロゲン化銀乳剤の層の少く
とも一つを支持体上にもつ感光材料を、画像的
露光の後にアルカリ性現像液によつて処理して
反転画像を得る方法、
ここにR10は水素原子、アルキル基、アリー
ル基、ヘテロ環基、１級、２級ないしは３級ア
ミノ基、アルコキシ基、アリールオキシ基、も
しくは複素環オキシ基を表わし、R11は水素原
子、ハロゲン原子、アルキル基、アルコキシ
基、アシルアミノ基を表わし、X-はアニオン
を表わし、ｍは１から５までの整数を表わす。
(2) 下記の一般式で表わされる化合物と組合わさ
れた、内部潜像型ハロゲン化銀乳剤層の少くと
も一つを支持体上にもつ感光材料を、画像的露
光の後にアルカリ性現像液によつて処理して反
転画像を得る方法、
ここにR12はシアノ基、ハロゲン原子、トリ
ハロメチル基を表わし、R11とｍは上記実施態
様(1)と同じ内容を表す。
(3) 前記一般式のR1とR2の少くとも一つが、
一般式のR1が炭素原子数の合計が８以上の
１個ないし２個のアルキル基を含む疎水性残基
をもつ化合物を用いる反転画像の作製方法。
(4) 前記の一般式のR10とR11の少くとも１つ
が、一般式ＶのR11が炭素原子数の合計が８以
上の１個ないし２個のアルキル基を含む疎水性
残基をもつ化合物を用いる反転画像の作製方
法。
(5) 前記の実施態様(3)、とりわけ実施態様(4)、に
規定された化合物を含む内部潜像ハロゲン化銀
の乳剤の層を少くとも一つもつ感光材料を、画
像的露光の後にアルカリ性現像液によつて処理
することによつて反転画像を作製する方法。
(6) 前記の実施態様(5)において該乳剤層が、現像
薬の酸化物と反応して色素像を形成する物質と
組合つている感光材料を処理して反転色素画像
を作製する方法。
(7) 前記の実施態様(6)において、色素像を形成す
る物質がカプラーであり、現像薬が芳香族一級
アミン・カラー現像薬である反転色素画像の作
製方法。
(8) 前記の実施態様(6)において、色素像を形成す
る物質が拡散性色素レリーサーであり、現像薬
が電子移動剤である拡散転写による反転色素画
像を作製する方法。[Table] The composition of the treatment liquid used here was that of the treatment liquid of Example 1 with the addition and dispersion of 150 g of carbon black. Compound 54 used in this example was synthesized as follows. (1) N-hexadecylnicotinamide 30.7 g of cetylamine and 33.2 g of pyridine are dispersed in 200 ml of acetonitrile, and 25 g of nicotinic acid chloride hydrochloride is added under water cooling. After further reacting at 55°C for 3 hours, 800 ml of water was added to collect the formed crystals. Recrystallization from 500 ml of ethanol yielded 36.3 g of the desired product. melting point 85
-7℃. Elemental analysis results C76.1%, H11.1%,
N8.0% (calculated value for C22H38N2O is C76.3
%, H11.1%, N8.1%). (2) 3-N-hexadecylcarbamoyl-1-phenacylpyridinium bromide (compound 54) 10.4 g of N-hexadecyl nicotinamide and 6.0 g of phenacyl bromide were dissolved in 100 ml of benzene at 80%
Incubate at ℃ for 7 hours. If you let it cool, crystals will precipitate, so add 100 ml of hexane to crystallize, and then collect the desired product. Yield: 15.4g. melting point
110-127℃ (flowing temperature). Elemental analysis results
C65.7%, H8.4%, N5.3 % ( calculated values for C30H45BrN2O2 are C66.0%, H8.3%, N5.1%). Preferred specific embodiments of the present invention are as follows. (1) A light-sensitive material having on a support at least one layer of an internal latent image type silver halide emulsion combined with a compound represented by the following general formula is subjected to an alkaline developer after imagewise exposure. A method of processing to obtain an inverted image, Here, R 10 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a primary, secondary or tertiary amino group, an alkoxy group, an aryloxy group, or a heterocyclic oxy group, and R 11 represents a hydrogen atom, It represents a halogen atom, an alkyl group, an alkoxy group, or an acylamino group, X - represents an anion, and m represents an integer from 1 to 5. (2) A light-sensitive material having on a support at least one internal latent image type silver halide emulsion layer combined with a compound represented by the following general formula is treated with an alkaline developer after imagewise exposure. how to obtain an inverted image by processing Here, R 12 represents a cyano group, a halogen atom, or a trihalomethyl group, and R 11 and m represent the same content as in the above embodiment (1). (3) At least one of R 1 and R 2 in the above general formula is
A method for producing a reversal image using a compound in which R 1 of the general formula has a hydrophobic residue containing one or two alkyl groups having a total number of carbon atoms of 8 or more. (4) At least one of R 10 and R 11 in the above general formula is a hydrophobic residue in which R 11 in the general formula V contains one or two alkyl groups having a total number of carbon atoms of 8 or more. A method for creating inverted images using compounds with (5) After imagewise exposure, a light-sensitive material having at least one layer of an internal latent image silver halide emulsion containing a compound as defined in embodiment (3) above, in particular embodiment (4), A method of producing a reversal image by processing with an alkaline developer. (6) A method of producing a reversal dye image by processing a light-sensitive material according to the above embodiment (5), in which the emulsion layer is combined with a substance that reacts with an oxide of a developer to form a dye image. (7) A method for producing a reversal dye image according to the above embodiment (6), wherein the substance forming the dye image is a coupler and the developer is an aromatic primary amine color developer. (8) A method for producing a reversal dye image by diffusion transfer according to the above embodiment (6), wherein the substance forming the dye image is a diffusible dye releaser and the developer is an electron transfer agent.
第１図は反転画像の現像銀量の、露光（対数）
に対する関係を表わす。第２図は色素転写によつ
て得られる反転カラー像の透過濃度の、露光量
（対数）に対する関係を表わす。
Figure 1 shows the exposure (logarithm) of the developed silver amount of the reversed image.
represents the relationship to. FIG. 2 shows the relationship between the transmission density of a reversal color image obtained by dye transfer and the exposure amount (logarithm).
Claims (1)
成するハロゲン化銀写真乳剤の少くとも１つを支
持体上にもつ感光材料を、画像露光の後に、下記
一般式〔〕又は〔〕で表わされる化合物から
選ばれる少くとも１の化合物を含有するアルカリ
性現像液によつて現像する方法。 式中、ｎは０、１、２もしくは３の整数を表わ
し、R1は３位、４位もしくは５位に位置する置
換基であつて、ハロゲン原子、トリハロメチル
基、シアノ基、カルバモイル基、カルボン酸エス
テル基、カルボンアミド基、スルフオンアミド
基、アシル基、スルフオニル基、スルフアモイル
基、アシルアミノ基、アリール基、アルキル基、
アルケニル基、ヘテロ環基よりなる群から選ばれ
る基を表わす。 但し、R1が４位の置換基である場合は、R1が
α−水素をもつアルキル基もしくはハロゲン原子
であることはない。 R2はアリール基、ヘテロ環基もしくはアルキ
ル基を表わす。Ｘはアニオン基を表わす。 ２ 下記一般式〔〕又は〔〕で表わされる化
合物から選ばれる少なくとも１つの化合物と組合
わされた、ハロゲン化銀粒子の内部に選択的に潜
像を形成するハロゲン化銀写真乳剤の層の少なく
とも１つを支持体上にもつ感光材料を画像露光の
後にアルカリ性現像液によつて現象する方法。 式中、ｎは０、１、２もしくは３の整数を表わ
し、R1は３位、４位もしくは５位に位置する置
換基であつて、ハロゲン原子、トリハロメチル
基、シアノ基、カルバモイル基、カルボン酸エス
テル基、カルボンアミド基、スルフオンアミド
基、アシル基、スルフオニル基、スルフアモイル
基、アシルアミノ基、アリール基、アルキル基、
アルケニル基、ヘテロ環基よりなる群から選ばれ
る基を表わす。 但し、R1が４位の置換基である場合は、R1は
α−水素をもつアルキル基もしくはハロゲン原子
であることはない。 R2はアリール基、ヘテロ環基もしくはアルキ
ル基を表わす。Ｘはアニオンを表わす。[Scope of Claims] 1. A photosensitive material having on a support at least one silver halide photographic emulsion that selectively forms a latent image inside silver halide grains is prepared by the following general formula after imagewise exposure. A method of developing with an alkaline developer containing at least one compound selected from the compounds represented by [ ] or [ ]. In the formula, n represents an integer of 0, 1, 2 or 3, and R 1 is a substituent located at the 3rd, 4th or 5th position, and is a halogen atom, trihalomethyl group, cyano group, carbamoyl group, Carboxylic acid ester group, carbonamide group, sulfonamide group, acyl group, sulfonyl group, sulfamoyl group, acylamino group, aryl group, alkyl group,
Represents a group selected from the group consisting of alkenyl groups and heterocyclic groups. However, when R 1 is a substituent at the 4-position, R 1 is not an alkyl group having α-hydrogen or a halogen atom. R 2 represents an aryl group, a heterocyclic group or an alkyl group. X represents an anion group. 2. At least one layer of a silver halide photographic emulsion that selectively forms a latent image inside silver halide grains, which is combined with at least one compound selected from the compounds represented by the following general formula [] or []. A method in which a photosensitive material having two layers on a support is developed using an alkaline developer after imagewise exposure. In the formula, n represents an integer of 0, 1, 2 or 3, and R 1 is a substituent located at the 3rd, 4th or 5th position, and is a halogen atom, trihalomethyl group, cyano group, carbamoyl group, Carboxylic acid ester group, carbonamide group, sulfonamide group, acyl group, sulfonyl group, sulfamoyl group, acylamino group, aryl group, alkyl group,
Represents a group selected from the group consisting of alkenyl groups and heterocyclic groups. However, when R 1 is a substituent at the 4-position, R 1 is not an alkyl group having α-hydrogen or a halogen atom. R 2 represents an aryl group, a heterocyclic group or an alkyl group. X represents an anion.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4694979A JPS55138742A (en) | 1979-04-17 | 1979-04-17 | Silver halide emulsion developing method |
| DE19803014628 DE3014628A1 (en) | 1979-04-17 | 1980-04-16 | METHOD FOR DEVELOPING A LIGHT-SENSITIVE MATERIAL |
| US06/140,923 US4324855A (en) | 1979-04-17 | 1980-04-16 | Process for developing a silver halide emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4694979A JPS55138742A (en) | 1979-04-17 | 1979-04-17 | Silver halide emulsion developing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55138742A JPS55138742A (en) | 1980-10-29 |
| JPS624699B2 true JPS624699B2 (en) | 1987-01-31 |
Family
ID=12761539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4694979A Granted JPS55138742A (en) | 1979-04-17 | 1979-04-17 | Silver halide emulsion developing method |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4324855A (en) |
| JP (1) | JPS55138742A (en) |
| DE (1) | DE3014628A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4789627A (en) * | 1906-07-02 | 1988-12-06 | Fuji Photo Film Co., Ltd. | Method for forming direct positive color images |
| JPS6073625A (en) * | 1983-09-30 | 1985-04-25 | Fuji Photo Film Co Ltd | Method for controlling re-reversal negative image in direct positive photosensitive silver halide material |
| EP0190512B1 (en) * | 1984-12-30 | 1992-09-30 | Konica Corporation | Positive image forming method |
| JPH0756565B2 (en) * | 1986-06-25 | 1995-06-14 | 富士写真フイルム株式会社 | Direct positive image forming method |
| EP0286593A3 (en) * | 1987-04-06 | 1989-09-06 | Ciba-Geigy Ag | Process for producing colour-positive masked images according to the silver dye-bleaching process |
| JP2604177B2 (en) * | 1987-10-05 | 1997-04-30 | 富士写真フイルム株式会社 | Direct positive color image forming method |
| US5384232A (en) * | 1991-12-02 | 1995-01-24 | E. I. Du Pont De Nemours And Company | Process for rapid access development of silver halide films using pyridinium as development accelerators |
| US6391899B1 (en) * | 1998-07-17 | 2002-05-21 | North Shore—Long Island Jewish Research Institute | Compounds and compositions for treating tissue ischemia |
| EP1220843A1 (en) * | 1999-10-06 | 2002-07-10 | Torrent Pharmaceuticals Ltd | Pyridinium derivatives for the treatment of diabetic and aging-related vascular complications |
| MXPA03005954A (en) * | 2000-12-29 | 2004-05-24 | Alteon Inc | Method for treating fibrotic diseases or other indications iiic. |
| CN104744351B (en) * | 2014-09-30 | 2017-06-06 | 三峡大学 | A kind of micromolecular inhibitor and the application on ornithine decarboxylase (ODC) is suppressed |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE502879A (en) * | 1950-04-29 | |||
| US3330655A (en) * | 1963-09-20 | 1967-07-11 | Eastman Kodak Co | Preparation of photographic direct positive color images |
| US3759901A (en) * | 1969-04-28 | 1973-09-18 | Eastman Kodak Co | Certain arylhydrazonalkyl quaternary salts |
| US3734738A (en) * | 1970-10-30 | 1973-05-22 | Eastman Kodak Co | Silver halide emulsions containing reactive quaternary salts nucleating agents |
| JPS523426A (en) * | 1975-06-27 | 1977-01-11 | Fuji Photo Film Co Ltd | Photosensitive material of direct positive halogenide silver |
| JPS5814665B2 (en) * | 1975-12-09 | 1983-03-22 | 富士写真フイルム株式会社 | Chiyokusetsupojihalogen Kaginkankouzairiyou |
-
1979
- 1979-04-17 JP JP4694979A patent/JPS55138742A/en active Granted
-
1980
- 1980-04-16 DE DE19803014628 patent/DE3014628A1/en active Granted
- 1980-04-16 US US06/140,923 patent/US4324855A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55138742A (en) | 1980-10-29 |
| DE3014628C2 (en) | 1991-05-02 |
| DE3014628A1 (en) | 1980-10-30 |
| US4324855A (en) | 1982-04-13 |
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